Synthesis and characterization of yttrium complexes bearing a bulky arylamido ancillary ligand

Shen, Bo; Ying, Liyan; Chen, Jue; Luo, Yunjie

doi:10.1016/j.ica.2007.08.010

Cited by 18 publications

(9 citation statements)

References 19 publications

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“…Complexes 1–3 were synthesized by the addition of a solution of the lithium salt LiN(SiPr i 3 )Dipp in diethyl ether to the corresponding anhydrous metal dichloride (Scheme ). The reaction mixtures for the formation of 1 and 3 were filtered, and the volume was decreased to ca.…”

Section: Resultsmentioning

confidence: 99%

“…The latter series is particularly noteworthy because it includes the only currently known, stable two-coordinate copper(II) complex where it is believed London dispersion forces are key to its stability . We therefore turned to a bulkier version of the so-called Wigley ligand -N(SiMe 3 )Dipp in which the -SiMe 3 substituent is replaced by the bulkier -SiPr i 3 group to afford the -N(SiPr i 3 )Dipp ligand that was first reported by Luo and co-workers . Several other ligands [-N(SiMe 3 ) 2 , -N(SiPh 2 Me) 2 , -C(SiMe 3 ) 3 , -OAr Ad 2 Me , -N(H)Ar Pr i 4 , -N(3,5-Xyl)Ad, and -N(SiMe 3 )Ad] (Ad = adamantyl; Ar Ad 2 Me = 2,6-diadamantyl-4-methylphenyl) were also tested with copper, but only -N(SiPr i 3 )Dipp and -N(SiPr i 3 )Dipp-4-Ad afforded signals consistent with the formation of their two-coordinate copper(II) complexes in solution.…”

Section: Introductionmentioning

confidence: 99%

“…3 )Dipp ligand that was first reported by Luo and co-workers. 8 -N(SiPh 2 Me) 2 , -C(SiMe 3 ) 3 , -OAr Ad 2 Me , -N(H)Ar Pr i 4 , -N(3,5-Xyl)Ad, and -N(SiMe 3 )Ad] (Ad = adamantyl; Ar Ad 2 Me = 2,6diadamantyl-4-methylphenyl) were also tested with copper, but only -N(SiPr i…”

Section: ■ Introductionmentioning

confidence: 99%

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Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

et al. 2019

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The synthesis and spectroscopic, structural, and magnetic characterization of the quasi-linear metal(II) bis(amides) M{N(SiPr i 3)Dipp}2 [Dipp = C6H3-2,6-Pr i 3; M = Fe (1), Co (2), or Zn (3)] are described. The magnetic data demonstrate the impact of metal ligand π-interactions on the magnetic properties of these two-coordinate transition metal amides. Disproportionation of the copper(I) amide species featuring the ligand -N(SiPr i 3)Dipp resulted in the decomposition product [(Pr i 3Si)N(c-C6H2-2,6-Pr i 2)]2 (4). The electron paramagnetic resonance spectrum of the unstable two-coordinate Cu{N(SiPr i 3)Dipp}2 displays significantly less Cu–N bond covalency than the stable two-coordinate copper(II) species Cu{N(SiMe3)Dipp}2. The testing of -N(SiPr i 3)Dipp and a range of other, related bulky amide ligands with their copper derivatives highlights the peculiar combination of steric and electronic properties of the Wigley ligand -N(SiMe3)Dipp that enable it to stabilize the unique two-coordinate copper(II) complex Cu{N(SiMe3)Dipp}2.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

et al. 2019

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“…Such simple complexes (NRR′) 2 Ln(alkyl) and (NRR′)Ln(alkyl) 2 coordinated by non-chelating alkyl and amido ligands, however, seem to be rather scarce. 40,41,56 Complexes 9-Ln display distorted tetrahedral coordination geometries as evidenced by large N1-Ln-C(µ 2 -CH 3 ) angles e.g., 9-La, 122.5(2)°; 9-Nd, 123.33(3)°( Table 3). Pronounced interactions of the Ln III metal centre with the amido ligand is also evidenced by close contacts to the ipso carbon atoms of the aryl rings (9-La, 2.791(7) Å; 9-Nd, 2.7502(9) Å).…”

Section: Reaction Of 7-ln With Ketonesmentioning

confidence: 99%

“…41 2.259(3) Å;56 6-Y, 2.172(4) Å). If the organoaluminum moieties in [NSiMe 3 (Ar)]Ln(AlMe 4 ) 2 (5-Ln) would be crucial for the formation of methylidene species, the reaction of the respective methylgallate [NSiMe 3 (Ar)]Y(GaMe 4 ) 2 (6-Y) with a Lewis base might yield a species like {[NSiMe 3 (Ar)]YMe 2 } x .…”

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Rare-earth metal methylidene complexes with Ln₃(μ₃-CH₂)(μ₃-Me)(μ₂-Me)₃core structure

et al. 2015

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Trinuclear rare-earth metal methylidene complexes with a Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3 structural motif were synthesized by applying three protocols. Polymeric [LuMe3]n (1-Lu) reacts with the sterically demanding amine H[NSiMe3(Ar)] (Ar = C6H3iPr2-2,6) in tetrahydrofuran via methane elimination to afford isolable monomeric [NSiMe3(Ar)]LuMe2(thf)2 (4-Lu). The formation of trinuclear rare-earth metal tetramethyl methylidene complexes [NSiMe3(Ar)]3Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3(thf)3 (7-Ln; Ln = Y, Ho, Lu) via reaction of [LnMe3]n (1-Ln; Ln = Y, Ho, Lu) with H[NSiMe3(Ar)] is proposed to occur via an "intermediate" species of the type [NSiMe3(Ar)]LnMe2(thf)x and subsequent C-H bond activation. Applying Lappert's concept of Lewis base-induced methylaluminate cleavage, compounds [NSiMe3(Ar)]Ln(AlMe4)2 (5-Ln; Ln = Y, La, Nd, Ho) were converted into methylidene complexes 7-Ln (Ln = Y, Nd, Ho) in the presence of tetrahydrofuran. Similarly, tetramethylgallate complex [NSiMe3(Ar)]Y(GaMe4)2 (6-Y) could be employed as a synthesis precursor for 7-Y. The molecular composition of complexes 4-Ln, 5-Ln, 6-Y and 7-Ln was confirmed by elemental analyses, FTIR spectroscopy, (1)H and (13)C NMR spectroscopy (except for holmium derivatives) and single-crystal X-ray diffraction. The Tebbe-like reactivity of methylidene complex 7-Nd with 9-fluorenone was assessed affording oxo complex [NSiMe3(Ar)]3Nd3(μ3-O)(μ2-Me)4(thf)3 (8-Nd). The synthesis of 5-Ln yielded [NSiMe3(Ar)]2Ln(AlMe4) (9-Ln; Ln = La, Nd) as minor side-products, which could be obtained in moderate yields when homoleptic Ln(AlMe4)3 were treated with two equivalents of K[NSiMe3(Ar)].

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Isolation and Reactivity of Stannylenoids Stabilized by Amido/Imino Ligands

Zhao

Fujimori

Kelly

et al. 2022

Chemistry A European J

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The reaction of the lithium aryl(silyl)amide Dipp(iPr3Si)NLi (Dipp=2,6‐iPr2C6H3) with one equivalent of SnCl2 in THF gave a novel stannylenoid Dipp(iPr3Si)NSnCl⋅LiCl(THF)2. Heating the solution of amidostannylenoid in toluene to 80 °C resulted in dimeric amido(chloro)stannylene [Dipp(iPr3Si)NSnCl]2, which can be converted to bis(amido)stannylene Sn[N(Dipp)(iPr3Si)]2 and amido(imino)stannylene Sn[N(Dipp)(iPr3Si)][IPrN] (IPrN=bis(2,6‐diisopropylphenyl)imidazolin‐2‐imino). Treatment of bis(imino)stannylenoid [IPrN]2Sn(Cl)Li with N2O resulted in the dimeric complex [IPrNSn(Cl)OLi]2. All compounds were characterized by NMR, elementary analysis, and X‐ray structural determination.

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Synthesis and characterization of yttrium complexes bearing a bulky arylamido ancillary ligand

Cited by 18 publications

References 19 publications

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Rare-earth metal methylidene complexes with Ln₃(μ₃-CH₂)(μ₃-Me)(μ₂-Me)₃core structure

Isolation and Reactivity of Stannylenoids Stabilized by Amido/Imino Ligands

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Synthesis and characterization of yttrium complexes bearing a bulky arylamido ancillary ligand

Cited by 18 publications

References 19 publications

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPri3)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPri3)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Rare-earth metal methylidene complexes with Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3core structure

Isolation and Reactivity of Stannylenoids Stabilized by Amido/Imino Ligands

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Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPrⁱ₃)Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

Rare-earth metal methylidene complexes with Ln₃(μ₃-CH₂)(μ₃-Me)(μ₂-Me)₃core structure